U.S. patent application number 17/321257 was filed with the patent office on 2021-11-18 for ester modified cross-linked silicone compositions.
The applicant listed for this patent is Momentive Performance Materials Inc.. Invention is credited to Benjamin FALK, Ashitha KANDIKKAL, Alok SARKAR.
Application Number | 20210355325 17/321257 |
Document ID | / |
Family ID | 1000005625985 |
Filed Date | 2021-11-18 |
United States Patent
Application |
20210355325 |
Kind Code |
A1 |
SARKAR; Alok ; et
al. |
November 18, 2021 |
ESTER MODIFIED CROSS-LINKED SILICONE COMPOSITIONS
Abstract
The present disclosures are directed to compositions comprising
a polymer having linear or branched silicone substituted by at
least one alkylcarboxy group and cross-linked with an alkyl
functional cross-linker, which has the benefits of compatibility
and structuring of personal care components and the resultant
personal care applications.
Inventors: |
SARKAR; Alok; (Bangalore,
IN) ; FALK; Benjamin; (Yorktown Heights, NY) ;
KANDIKKAL; Ashitha; (Bangalore, IN) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Momentive Performance Materials Inc. |
Waterford |
NY |
US |
|
|
Family ID: |
1000005625985 |
Appl. No.: |
17/321257 |
Filed: |
May 14, 2021 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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63026399 |
May 18, 2020 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C08G 77/20 20130101;
C08G 77/80 20130101; C08F 220/04 20130101; A61K 2800/10 20130101;
A61K 2800/95 20130101; A61K 8/042 20130101; C08F 230/08 20130101;
C08G 77/12 20130101; C08L 2312/00 20130101; C08G 77/08 20130101;
C08L 83/04 20130101; C08G 77/24 20130101 |
International
Class: |
C08L 83/04 20060101
C08L083/04; C08G 77/08 20060101 C08G077/08; C08G 77/12 20060101
C08G077/12; C08G 77/20 20060101 C08G077/20; C08G 77/24 20060101
C08G077/24; C08G 77/00 20060101 C08G077/00; C08F 230/08 20060101
C08F230/08; C08F 220/04 20060101 C08F220/04; A61K 8/04 20060101
A61K008/04 |
Claims
1. A composition comprising a polymer having linear or branched
silicone substituted by at least one alkylcarboxyalkyl group, and
cross-linked with an alkyl functional cross-linker, wherein an
average number of alkylcarboxyalkyl substitutions per silicone is
between 1 and 60 and an average number of crosslinks between linear
or branched silicone being between 1 and 30.
2. The composition of claim 1, wherein the average number of
alkylcarboxyalkyl substitutions per silicone is between 1 and
15.
3. (canceled)
4. The composition of claim 1, wherein the average number of
crosslinks between linear or branched silicones is between 1 and
15.
5. (canceled)
6. The composition of claim 1, wherein the polymer is prepared by a
method comprising reacting: (a) a Si--H functional compound of
formula (I):
M.sup.H.sub.aM.sub.bD.sup.H.sub.cD.sub.dT.sup.H.sub.eT.sub.fQ.sub.g
(I) wherein: M.sup.H=R.sup.1R.sup.2HSiO.sub.1/2;
M=R.sup.3R.sup.4R.sup.5SiO.sub.1/2; D.sup.H=R.sup.6HSiO.sub.2/2;
D=R.sup.7R.sup.8SiO.sub.2/2; T.sup.H=HSiO.sub.3/2;
T=R.sup.9SiO.sub.3/2; and Q=SiO.sub.4/2; wherein R.sup.2, R.sup.3,
R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, and R.sup.9 are
independently an aliphatic, aromatic, or fluoro monovalent
hydrocarbon having from 1 to 60 carbon atoms; and a, b, c, d, e, f,
and g are independently zero or a positive integer, such that 2
.ltoreq.a+b+c+d+e+f+g.ltoreq.6000 and when a'+c'+e'=2, a+c+e>2;
(b) a carboxy functional olefin of formula (II): ##STR00007##
wherein R' is hydrogen, --Si(R.sup.a).sub.3 wherein R.sup.a is an
aliphatic monovalent hydrocarbon, or an aliphatic, aromatic or
fluoro monovalent hydrocarbon; n is 0.ltoreq.n.ltoreq.30; and (c) a
silicone based alkenyl functional cross-linker of formula (III)
and/or a non-silicone based alkenyl functional cross-linker of
formula (IV):
M.sup.1.sub.a'M.sup.2.sub.b'D.sup.1.sub.c'D.sup.2.sub.d'T.sup.1.sub.e'T.s-
up.2.sub.f'Q.sub.g' (III), ##STR00008## wherein:
M.sup.1=R.sup.10R.sup.11R.sup.12SiO.sub.1/2;
M.sup.2=R.sup.13R.sup.14R.sup.15SiO.sub.1/2;
D.sup.1=R.sup.16R.sup.17SiO.sub.2/2;
D.sup.2=R.sup.18R.sup.19SiO.sub.2/2; T.sup.1=R.sup.20SiO.sub.3/2;
T.sup.2=R.sup.21SiO.sub.3/2; and Q=SiO.sub.4/2; wherein R.sup.11,
R.sup.12, R.sup.13, R.sup.14, R.sup.15, R.sup.17, R.sup.18,
R.sup.19, and R.sup.21,a re independently an aliphatic, aromatic,
or fluoro monovalent hydrocarbon having from 1 to 60 carbon atoms;
R.sup.10, R.sup.16, and R.sup.20 are each a monovalent radical
containing at least one terminal olefin bond; a', b', c', d', e',
f', and g' are independently zero or a positive integer, such that
2.ltoreq.a'+b'+c'+d'+e'+f'+g'.ltoreq.6000 and when a+c+e=2,
a'+c'+e'>2; and Z is an aliphatic hydrocarbon with 1 to 60
carbon atoms.
7. The composition of claim 6, wherein the one or more of R.sup.1,
R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, and
R.sup.9 is a C.sub.1-C.sub.20 monovalent hydrocarbon.
8. (canceled)
9. The composition of claim 6, wherein a, b, c, d, e, f, and g are
2.ltoreq.a+b+c+d+e+f+g.ltoreq.4000.
10.-12. (canceled)
13. The composition of claim 6, wherein R' is R.sup.1 or a
combination of R.sup.1, hydrogen, and --Si(R.sup.a).sub.3 wherein
R.sup.a is an aliphatic monovalent hydrocarbon.
14.-20. (canceled)
21. The composition of claim 6, wherein one or more of R.sup.11,
R.sup.12, R.sup.13, R.sup.14, R.sup.15, R.sup.17, R.sup.18,
R.sup.19, and R.sup.21 is a C.sub.1-C.sub.30 monovalent
hydrocarbon.
22.-24. (canceled)
25. The composition of claim 6, wherein one or more of R.sup.11,
R.sup.12, R.sup.13, R.sup.14, R.sup.15, R.sup.17, R.sup.18,
R.sup.19, and R.sup.21 is an aromatic monovalent hydrocarbon.
26. (canceled)
27. The composition of claim 6, wherein one or more of R.sup.11,
R.sup.12, R.sup.13, R.sup.14, R.sup.15, R.sup.17, R.sup.18,
R.sup.19, and R.sup.21 is a fluoro monovalent hydrocarbon.
28. (canceled)
29. The composition of claim 6, wherein Z is --(CHR.sup.22).sub.m--
or --(CH.sub.2CHR.sup.23O).sub.k--, wherein m and k are positive
integers, such that 1.ltoreq.m.ltoreq.60 and 1.ltoreq.k.ltoreq.500,
and R.sup.22 and R.sup.23 are independently hydrogen or monovalent
hydrocarbon having from 1 to 60 carbon atoms.
30.-39. (canceled)
40. The composition of claim 1, wherein the polymer is in a pure
carboxy alkyl ester form.
41. The composition of claim 1, wherein the polymer is in
combination of a carboxy alkyl ester and salt (or acid) form.
42.-44. (canceled)
45. A method for preparing a polymer comprising reacting: (a) a
Si--H functional compound of formula (I):
M.sup.H.sub.aM.sub.bD.sup.H.sub.cD.sub.dT.sup.H.sub.eT.sub.fQ.sub.g
(I) wherein: M.sup.H=R.sup.1R.sup.2HSiO.sub.1/2;
M=R.sup.3R.sup.4R.sup.5SiO.sub.1/2; D.sup.H=R.sup.6HSiO.sub.2/2;
D=R.sup.7R.sup.8SiO.sub.2/2; T.sup.H=HSiO.sub.3/2;
T=R.sup.9SiO.sub.3/2; and Q=SiO.sub.4/2; wherein R.sup.1, R.sup.2,
R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, and R.sup.9
are independently an aliphatic, aromatic, or fluoro monovalent
hydrocarbon having from 1 to 60 carbon atoms; and a, b, c, d, e, f,
and g are independently zero or a positive integer, such that 2
.ltoreq.a+b+c+d+e+f+g.ltoreq.6000 and when a'+c'+e'=2, a+c+e>2;
(b) a carboxy functional olefin of formula (II): ##STR00009##
wherein R' is hydrogen, --Si(R.sup.a).sub.3 wherein R.sup.a is an
aliphatic monovalent hydrocarbon, an aliphatic, aromatic or fluoro
monovalent hydrocarbon; n is 0.ltoreq.n.ltoreq.30; and (c) a
silicone based alkenyl functional cross-linker of formula (III)
and/or a non-silicone based alkenyl functional cross-linker of
formula (IV):
M.sup.1.sub.a'M.sup.2.sub.b'D.sup.1.sub.c'D.sup.2.sub.d'T.sup.1.sub.e'T.s-
up.2.sub.f'Q.sub.g' (III), ##STR00010## wherein:
M.sup.1=R.sup.10R.sup.11R.sup.12SiO.sub.1/2;
M.sup.2=R.sup.13R.sup.14R.sup.15SiO.sub.1/2;
D.sup.1=R.sup.16R.sup.17SiO.sub.2/2;
D.sup.2=R.sup.18R.sup.19SiO.sub.2/2; T.sup.1=R.sup.20SiO.sub.3/2;
T.sup.2=R.sup.21SiO.sub.3/2; and Q=SiO.sub.4/2; wherein R.sup.11,
R.sup.12, R.sup.13, R.sup.14, R.sup.15, R.sup.17, R.sup.18,
R.sup.19, and R.sup.21, are independently an aliphatic, aromatic,
or fluoro monovalent hydrocarbon having from 1 to 60 carbon atoms;
R.sup.10, R.sup.16, and R.sup.20 are each a monovalent radical
containing at least one terminal olefin bond; a', b', c', d', e',
f', and g' are independently zero or a positive integer, such that
2.ltoreq.a'+b'+c'+d'+e'+f'+g'.ltoreq.6000 and when a+c+e=2,
a'+c'+e'>2; and Z is an aliphatic hydrocarbon with 1 to 60
carbon atoms.
46. The method of claim 45, wherein one or more of R.sup.1,
R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, and
R.sup.9 is a C.sub.1-C.sub.20 monovalent hydrocarbon.
47.-51. (canceled)
52. The method of claim 45, wherein R' is R.sup.1 or a combination
of R.sup.1, hydrogen, and --Si(R.sup.a).sub.3 wherein R.sup.a is an
aliphatic monovalent hydrocarbon.
53.-59. (canceled)
60. The method of claim 45, wherein one or more R.sup.11, R.sup.12,
R.sup.13, R.sup.14, R.sup.15, R.sup.17, R.sup.18, R.sup.19, and
R.sup.21 is a C.sub.1-C.sub.60 monovalent hydrocarbon.
61.-67. (canceled)
68. The method of claim 45, wherein Z group is
--(CHR.sup.22).sub.m-- or --(CH.sub.2CHR.sup.23O).sub.k--, wherein
m and k are positive integers, such that 1.ltoreq.m.ltoreq.60 and
1.ltoreq.k.ltoreq.500, and R.sup.22 and R.sup.23 are independently
hydrogen or monovalent hydrocarbon having from 1 to 60 carbon
atoms.
69.-78. (canceled)
79. The method of claim 45, wherein the polymer is in a pure
carboxy alkyl ester form.
80. The method of claim 45, wherein the polymer is in combination
of a carboxy alkyl ester and salt (or acid) form.
81. (canceled)
82. The method of claim 45, wherein the reaction between the Si--H
compound of formula (I), the carboxy functional olefin of formula
(II) and the alkenyl functional cross-linker of formula (III)
and/or (IV) occurs in the presence of at least one precious metal
catalyst selected from the group consisting of a rhodium,
ruthenium, palladium, osmium, iridium, iron and platinum
catalyst.
83.-84. (canceled)
85. A personal care composition comprising: (a) the composition of
claim 1; and (b) one or more personal care components.
86.-89. (canceled)
Description
BACKGROUND
Field
[0001] This invention relates to compositions comprising a polymer
having linear or branched silicone substituted by at least one
alkylcarboxy group and cross-linked with an alkyl functional
cross-linker. In one aspect, personal care compositions containing
such carboxyl functional silicone networks are provided herein.
Background
[0002] Silicone gels are commonly added in a variety of personal
care formulations to enhance their aesthetics with respect to
sensory, texture, rheology and optical performance. However,
traditional silicone gels have limited versatility in terms of
compatibility with polar solvents such as hydrocarbon oils,
plant-based oils, glycerin and water. Moreover, most of these gels
often fail to retain their texture and rheological benefits at
lower dosage. Therefore, there exists a need for a silicone gel
composition with improved compatibility, texture and rheological
performance.
BRIEF SUMMARY OF THE DISCLOSURE
[0003] Compositions comprising a polymer having linear or branched
silicone substituted by at least one alkylcarboxy group in a free
or salt form and cross-linked with an alkyl functional
cross-linker, wherein an average number of alkylcarboxy
substitutions per silicone is between 1 and 60 and an average
number of crosslinks between linear or branched silicones being
between 1 and 30 are described herein. In some aspects, the polymer
is a linear polymer. In some aspects, the polymer is a branched
polymer.
[0004] In some aspects, the average number of alkylcarboxy
substitutions per silicone is between 1 and 15. In some aspects,
the average number of alkylcarboxy substitutions per silicone is
between 1 and 12. In some aspects, the average number of crosslinks
between linear or branched silicones is between 1 and 15. In some
aspects, the average number of crosslinks between linear or
branched silicones is between 1 and 12.
[0005] In some aspects, the polymer is prepared by a method
comprising reacting:
[0006] (a) a Si--H functional compound of formula (I):
M.sup.H.sub.aM.sub.bD.sup.H.sub.cD.sub.dT.sup.H.sub.eT.sub.fQ.sub.g
(I)
[0007] wherein: [0008] M.sup.H=R.sup.1R.sup.2HSiO.sub.1/2; [0009]
M=R.sup.3R.sup.4R.sup.5SiO.sub.1/2; [0010]
D.sup.H=R.sup.6HSiO.sub.2/2; [0011] D=R.sup.7R.sup.8SiO.sub.2/2;
[0012] T.sup.H=HSiO.sub.3/2; [0013] T=R.sup.9SiO.sub.3/2; and
[0014] Q=SiO.sub.4/2;
[0015] wherein [0016] R.sup.1,R.sup.2, R.sup.3, R.sup.4, R.sup.5,
R.sup.6, R.sup.7, R.sup.8, and R.sup.9 are independently an
aliphatic, aromatic, or fluoro monovalent hydrocarbon having from 1
to 60 carbon atoms; and [0017] a, b, c, d, e, f, and g are
independently zero or a positive integer, such that
2.ltoreq.a+b+c+d+e+f+g.ltoreq.6000 and when a'+c'+e'=2,
a+c+e>2;
[0018] (b) a carboxy functional olefin of formula (II):
##STR00001##
[0019] wherein [0020] R' is hydrogen, --Si(R.sup.a).sub.3 wherein
R.sup.a is an aliphatic monovalent hydrocarbon, or an aliphatic,
aromatic or fluoro monovalent hydrocarbon; [0021] n is
0.ltoreq.n.ltoreq.30; and
[0022] (c) a silicone based alkenyl functional cross-linker of
formula (III) and/or a non-silicone based alkenyl functional
cross-linker of formula (IV):
M.sup.1.sub.a'M.sup.2.sub.b'D.sup.1.sub.c'D.sup.2.sub.d'T.sup.1.sub.e'T.-
sup.2.sub.f'Q.sub.g' (III),
##STR00002##
[0023] wherein: [0024] M.sup.1=R.sup.10R.sup.11R.sup.12SiO.sub.1/2;
[0025] M.sup.2=R.sup.13R.sup.14R.sup.15SiO.sub.1/2; [0026]
D.sup.1=R.sup.16R.sup.17SiO.sub.2/2; [0027]
D.sup.2=R.sup.18R.sup.19SiO.sub.2/2; [0028]
T.sup.1=R.sup.20SiO.sub.3/2; [0029] T.sup.2=R.sup.21SiO.sub.3/2;
and [0030] Q=SiO.sub.4/2;
[0031] wherein [0032] R.sup.11, R.sup.12, R.sup.13, R.sup.14,
R.sup.15, R.sup.17, R.sup.18, R.sup.19, and R.sup.21, are
independently an aliphatic, aromatic, or fluoro monovalent
hydrocarbon having from 1 to 60 carbon atoms; [0033] R.sup.10,
R.sup.16, and R.sup.20 are each a monovalent radical containing at
least one terminal olefin bond wherein a', b', c', d', e', f', and
g' are independently zero or a positive integer, such that
2.ltoreq.a'+b'+c'+d'+e'+f'+g.ltoreq.'6000 and when a+c+e=2,
a'+c'+e'>2; and [0034] Z is an aliphatic hydrocarbon with 1 to
60 carbon atoms.
[0035] The polymer can be prepared by mixing the components in any
order. Additionally, each component can be added simultaneously or
sequentially, or as batch or semi-batch preparations.
[0036] The disclosure also relates to methods for preparing the
polymer comprising reacting:
[0037] (a) a Si--H functional compound of formula (I):
M.sup.H.sub.aM.sub.bD.sup.H.sub.cD.sub.dT.sup.H.sub.eT.sub.fQ.sub.g
(I)
[0038] wherein: [0039] M.sup.H=R.sup.1R.sup.2HSiO.sub.1/2; [0040]
M=R.sup.3R.sup.4R.sup.5SiO.sub.1/2; [0041]
D.sup.H=R.sup.6HSiO.sub.2/2; [0042] D=R.sup.7R.sup.8SiO.sub.2/2;
[0043] T.sup.H=HSiO.sub.3/2; [0044] T=R.sup.9SiO.sub.3/2; and
[0045] Q=SiO.sub.4/2;
[0046] wherein [0047] R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5,
R.sup.6, R.sup.7, R.sup.8, and R.sup.9 are independently an
aliphatic, aromatic, or fluoro monovalent hydrocarbon having from 1
to 60 carbon atoms; and [0048] a, b, c, d, e, f, and g are
independently zero or a positive integer, such that
2.ltoreq.a+b+c+d+e+f+g.ltoreq.6000 and when a'+c'+e'=2,
a+c+e>2;
[0049] (b) a carboxy functional olefin of formula (II):
##STR00003##
[0050] wherein [0051] R' is hydrogen, --Si(R.sup.a).sub.3 wherein
R.sup.a is an aliphatic monovalent hydrocarbon, or an aliphatic,
aromatic or fluoro monovalent hydrocarbon; [0052] n is
0.ltoreq.n.ltoreq.30; and
[0053] (c) a silicone based alkenyl functional cross-linker of
formula (III) and/or a non-silicone based alkenyl functional
cross-linker of formula (IV):
M.sup.1.sub.a'M.sup.2.sub.b'D.sup.1.sub.c'D.sup.2.sub.d'T.sup.1.sub.e'T.-
sup.2.sub.f'Q.sub.g' (III),
##STR00004##
[0054] wherein: [0055] M.sup.1=R.sup.10R.sup.11R.sup.12SiO.sub.1/2;
[0056] M.sup.2=R.sup.13R.sup.14R.sup.15SiO.sub.1/2; [0057]
D.sup.1=R.sup.16R.sup.17SiO.sub.2/2; [0058]
D.sup.2=R.sup.18R.sup.19SiO.sub.2/2; [0059]
T.sup.1=R.sup.20SiO.sub.3/2; [0060] T.sup.2=R.sup.21SiO.sub.3/2;
and [0061] Q=SiO.sub.4/2;
[0062] wherein [0063] R.sup.11, R.sup.12, R.sup.13, R.sup.14,
R.sup.15, R.sup.17, R.sup.18, R.sup.19, and R.sup.21, are
independently an aliphatic, aromatic, or fluoro monovalent
hydrocarbon having from 1 to 60 carbon atoms; [0064] R.sup.10,
R.sup.16 and R.sup.20 are each a monovalent radical containing at
least one terminal olefin bond; [0065] a', b', c', d', e', f', and
g' are independently zero or a positive integer, such that
2.ltoreq.a'+b'+c'+d'+e'+f'+g'.ltoreq.6000 and when a+c+e=2,
a'+c'+e'>2; and [0066] Z is an aliphatic hydrocarbon with 1 to
60 carbon atoms.
[0067] The polymer can be prepared by mixing the components in any
order. Additionally, each component can be added simultaneously or
sequentially, or as batch or semi-batch preparations.
[0068] In some aspects, the reaction between the Si--H compound of
formula (I), the carboxy functional olefin of formula (II) and the
alkenyl functional cross-linker of formula (III) and/or (IV) occurs
in the presence of at least one precious metal catalyst selected
from the group consisting of a rhodium, ruthenium, palladium,
osmium, iridium, iron, and platinum catalyst. In some aspects, at
least one of the platinum catalysts is selected from the group
consisting of (PtCl2Olefin), H(PtCl3Olefin), platinic chloride,
chloroplatinic acid, bis(acetylacetonato)platinum,
(.eta.15-Cyclopentadienyl)trialkylplatinum,
1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene-1,3-divinyl-1,1,3,3-tetr-
amethyldisiloxaneplatinum(0),
1,3-bis(cyclohexyl)imidazole-2-ylidene-1,3-divinyl
-1,1,3,3-tetramethyldisiloxaneplatinum(0), Pt.sub.2(dba).sub.3,
Pt.sub.2(dvs).sub.3, Pt(OAc).sub.2, Pt(acac).sub.2,
Na.sub.2PtCl.sub.6, K.sub.2PtCl.sub.6, platinum carbonate, platinum
nitrate, 1,5-cyclooctadienedimethylplatinum(II), platinum
perchlorate, amine complexes of the platinum ammonium
hexachloropalladate(IV), a cyclopropane complex of platinum
chloride, and a complex formed from chloroplatinic acid.
[0069] In some aspects, one or more of R.sup.1, R.sup.2, R.sup.3,
R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, and R.sup.9 is an
aliphatic, aromatic, or fluoro monovalent hydrocarbon. In some
aspects, one or more of R.sup.1, R.sup.2, R.sup.3, R.sup.4,
R.sup.5, R.sup.6, R.sup.7, R.sup.8, and R.sup.9 is a
C.sub.1-C.sub.60 monovalent hydrocarbon. In some aspects, one or
more of R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6,
R.sup.7, R.sup.8, and R.sup.9 is a C.sub.1-C.sub.20 monovalent
hydrocarbon. In some aspects, one or more of R.sup.1, R.sup.2,
R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, and R.sup.9
is a C.sub.1-C.sub.8 monovalent hydrocarbon.
[0070] In some aspects, a, b, c, d, e, f, and g are
2.ltoreq.a+b+c+d+e+f+g.ltoreq.4000. In some aspects, a, b, c, d, e,
f, and g are 2.ltoreq.a+b+c+d+e+f+g.ltoreq.2000. In some aspects,
a, c, and e are 2.ltoreq.a+c+e.ltoreq.120. In some aspects, a, c,
and e are 2.ltoreq.a+c+e.ltoreq.100.
[0071] In some aspects, R' is R.sup.1 or a combination of R.sup.1
and --Si(R.sup.a).sub.3 wherein R.sup.a is an aliphatic monovalent
hydrocarbon. In some aspects, R.sup.a is a C.sub.1-C.sub.12 group.
In some aspects, R.sup.a is a C.sub.1-C.sub.8 group. In some
aspects, R.sup.a is selected from the group consisting of methyl,
ethyl, propyl, butyl, pentyl, hexyl, and heptyl. In some aspects,
R.sup.a is methyl. In some aspects, R' is ethyl. In some aspects,
R' is heptyl. In some aspects, R' is hydrogen.
[0072] In some aspects, R.sup.11, R.sup.12, R.sup.13, R.sup.14,
R.sup.15, R.sup.17, R.sup.18, R.sup.19, and R.sup.21, are
independently an aliphatic, aromatic, or fluoro monovalent
hydrocarbon having from 1 to 60 carbon atoms. In some aspects, one
or more of R.sup.11, R.sup.12, R.sup.13, R.sup.14, R.sup.15,
R.sup.17, R.sup.18, R.sup.19, and R.sup.21 is a C.sub.1-C.sub.30
monovalent hydrocarbon. In some aspects, one or more of R.sup.11,
R.sup.12, R.sup.13, R.sup.14, R.sup.15, R.sup.17, R.sup.18,
R.sup.19, and R.sup.21 is a C.sub.1-C.sub.18 monovalent
hydrocarbon.
[0073] In some aspects, one or more of R.sup.11, R.sup.12,
R.sup.13, R.sup.14, R.sup.15, R.sup.17, R.sup.18, R.sup.19, and
R.sup.21 is an aliphatic monovalent hydrocarbon. In some aspects,
one or more of R.sup.11, R.sup.12, R.sup.13, R.sup.14, R.sup.15,
R.sup.17, R.sup.18, R.sup.19, and R.sup.21 is selected from the
group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl,
isobutyl, tert-butyl, n-pentyl, isopentyl, neo-pentyl, tert-pentyl,
hexyl, heptyl, octyl, nonyl, decyl, and cycloalkyl. In some
aspects, one or more of R.sup.11, R.sup.12, R.sup.13, R.sup.14,
R.sup.15, R.sup.17, R.sup.18, R.sup.19, and R.sup.21 is selected
from the group consisting of n-hexyl, n-heptyl, n-octyl, isooctyl,
2,2,4-trimethylpentyl, n-nonyl, n-decyl, cyclopentyl, cyclohexyl,
cycloheptyl, and methylcyclohexyl.
[0074] In some aspects, one or more of R.sup.11, R.sup.12,
R.sup.13, R.sup.14, R.sup.15, R.sup.17, R.sup.18, R.sup.19, and
R.sup.21 is an aromatic monovalent hydrocarbon. In some aspects,
one or more of R.sup.11, R.sup.12, R.sup.13, R.sup.14, R.sup.15,
R.sup.17, R.sup.18, R.sup.19, and R.sup.21 is selected from the
group consisting of phenyl, naphthyl, o-tolyl, m-tolyl, p-tolyl,
xylyl, ethylphenyl, and benzyl.
[0075] In some aspects, one or more of R.sup.11, R.sup.12,
R.sup.13, R.sup.14, R.sup.15, R.sup.17, R.sup.18, R.sup.19, and
R.sup.21 is a fluoro monovalent hydrocarbon.
[0076] In some aspects, a'=2, d'=75-600, and b'=c'=e'=f'=g'=0. In
some aspects, a', c', and e' are 2.ltoreq.a'+c'+e'.ltoreq.120. In
some aspects, a', c', and e' are 2.ltoreq.a'+c'+e'.ltoreq.100. In
some aspects, a=12, b=c=d=e=f=0, g=10, and n=8. In some aspects,
b=2, c=36, a=d=e=f=g=0, and n=8. In some aspects, a=3, b=c=d=e=g=0,
f=1, and n=8.
[0077] In some aspects, Z is --(CHR.sup.22).sub.m-- or
--(CH.sub.2CHR.sup.23O).sub.k--, and m and k are positive integers,
such that 1.ltoreq.m.ltoreq.60 and 1.ltoreq.k.ltoreq.500, and
R.sup.22 and R.sup.23 are independently hydrogen or monovalent
hydrocarbon having from 1 to 60 carbon atoms. In some aspects, Z is
--(CHR.sup.22).sub.m--, m is 1-30, and R.sup.22 is from 1 to 30
carbon atoms. In some aspects, Z is --(CHR.sup.22).sub.m--, m is
1-18, and R.sup.16 is from 1 to 20 carbon atoms. In some aspects, Z
is --(CH.sub.2CHR.sup.23O).sub.k--, k is 1-250, and R.sup.23 is
from 1 to 30 carbon atoms. In some aspects, Z is
--(CH.sub.2CHR.sup.23O).sub.k--k is 1-100, and R.sup.23 is from 1
to 20 carbon atoms.
[0078] In some aspects, the polymer is in a pure carboxy alkyl
ester form. In some aspects, the polymer is in combination of a
carboxy alkyl ester and salt (or acid) form. In some aspects, a
cation of the salt form is independently selected from alkali
metals, alkaline earth metals, transition metals, rare earth
metals, metals, metal complexes, quaternary ammonium and
phosphonium groups, organic cations, alkyl cations, cationic
hydrocarbons, cationic polymers, or zwitterions.
[0079] The disclosure also relates to a product prepared by any of
the methods described herein.
[0080] The disclosure additionally relates to personal care
compositions comprising (a) a composition or product described
herein; and (b) one or more personal care components.
[0081] In some aspects, the one or more personal care components
are selected from the group consisting of a humectant, emollient,
moisturizer, pigment, colorant, fragrance, biocide, preservative,
antioxidant, anti-fungal agent, antiperspirant agent, exfoliant,
hormone, enzyme, medicinal compound, vitamin, salt, electrolyte,
alcohol, polyol, absorbing agent for ultraviolet radiation,
botanical extract, surfactant, silicone oil, organic oil, wax, film
former, and thickening agent. In some aspects, the one or more
emollients is selected from the group consisting of triglyceride
esters, wax esters, alkyl or alkenyl ester of fatty acids,
polyhydric alcohol esters, and mixtures thereof. In some aspects,
the one or more personal care components is a silicone oil, an
organic oil, or mixtures thereof.
[0082] The disclosure further relates to a personal care
application comprising a personal care component described herein,
wherein the personal care application is selected from the group
consisting of a deodorant, antiperspirant,
antiperspirant/deodorant, shaving product, skin lotion,
moisturizer, toner, bath product, cleansing product, hair care
product, manicure product, protective cream, and color
cosmetic.
DETAILED DESCRIPTION
Definitions and Abbreviations
[0083] As used above, and throughout the description, the following
terms, unless otherwise indicated, shall be understood to have the
following meanings.
[0084] Unless stated otherwise, the terms "a" and "an" and "the"
and similar references used in the context of describing a
particular aspect of the application (especially in the context of
claims) can be construed to cover both the singular and the plural.
The recitation of ranges of values herein is merely intended to
serve as a shorthand method of referring individually to each
separate value falling within the range. Unless otherwise indicated
herein, each individual value is incorporated into the
specification as if it were individually recited herein.
[0085] The term "carboxy" means the radical --C(O)O--. It is noted
that compounds described herein containing carboxy moiety can
include protected derivatives thereof, i.e., where the oxygen is
substituted with a protecting group. Suitable protecting groups for
carboxy moieties include benzyl, tert-butyl, methyl, ethyl, and the
like. The term "carboxyl" means --COOH.
[0086] The term "polymer" means a substance, chemical compound or
mixture of compounds, that has a molecular structure consisting
chiefly or entirely of a large number of similar units (e.g.,
monomer units) bonded together.
[0087] It will be further understood that any compound, material or
substance which is expressly or implicitly disclosed in the
specification and/or recited in a claim as belonging to a group of
structurally, compositionally and/or functionally related
compounds, materials or substances includes individual
representatives of the group and all combinations thereof.
[0088] The term "aliphatic monovalent hydrocarbon" as used herein,
means hydrocarbon which is completely saturated and is not
aromatic. For example, suitable aliphatic groups include linear
alkyl groups. A "fluoro monovalent hydrocarbon" means a completely
saturated hydrocarbon that is substituted with a fluoro atom.
[0089] The term "pure" as used herein, means free of any
contamination or not mixed or adulterated with any other substance
or material. For example, a pure carboxy alkyl ester form refers to
a substance, material, or polymer with at least one ester
functional group only.
[0090] The term "hydrocarbon" means any hydrocarbon group from
which one or more hydrogen atoms has been removed and is inclusive
of alkyl, alkenyl, alkynyl, cyclic alkyl, cyclic alkenyl, cyclic
alkynyl, aryl, aralkyl and arenyl and may contain heteroatoms.
[0091] The term "alkyl" means any monovalent, saturated straight,
branched or cyclic hydrocarbon group. Examples of "alkyl" groups
include methyl, ethyl, isopropyl, and the like.
[0092] The term "aromatic" refer to an optionally substituted
C.sub.6-14 aromatic hydrocarbon moiety comprising one to three
aromatic rings. In at least one aspect, the aromatic group is a
C.sub.6-10 aryl group. Aromatic groups include, without limitation,
phenyl. The term "aromatic" can be used interchangeably with the
terms "aryl group," "aryl ring," and "aryl."
[0093] In describing the products as a reaction product of initial
materials, reference is made to the initial species recited and it
is to be noted that additional materials can be added to the
initial mixture of synthetic precursors. These additional materials
can be reactive or non-reactive. The defining characteristic is
that the reaction product can be obtained from the reaction of at
least the components listed as disclosed. Non-reactive components
can be added to the reaction mixture as diluents or to impart
additional properties unrelated to the properties of the
composition prepared as a reaction product. Thus, for example
particulate solids, such as pigments, can be dispersed into the
reaction mixture, before, during, or after the reaction to produce
a reaction product composition that additionally comprises the
non-reactive component. Additional reactive components can also be
added. Such components can react with the initial reactants or they
can react with the reaction product. The phrase "reaction product"
is intended to include those possibilities, as well as including
the addition of non-reactive components.
[0094] The expression "shearing" as used herein means the silicone
composition can be further processed to adjust the viscosity and
sensory feel of the composition. This can be achieved, for example,
by subjecting the composition to a moderate to high shearing
force.
[0095] As used herein, the term "non-aqueous hydroxylic organic
compound" or "non-aqueous hydroxylic solvent" means hydroxyl
containing organic compounds such as, but not limited to, alcohols,
glycols, polyhydric alcohols and polymeric glycols and mixtures
thereof, that are liquid at room temperature, e.g. about 25.degree.
C., and about one atmosphere pressure.
Polymeric Compositions
[0096] Compositions comprising a polymer having linear or branched
silicone substituted by at least one alkylcarboxy group in a free
or salt form and cross-linked with an alkyl functional
cross-linker, wherein an average number of alkylcarboxy
substitutions per silicone is between 1 and 60 and an average
number of crosslinks between linear or branched silicones being
between 1 and 30 are described herein. In some aspects, the polymer
is a linear polymer. In some aspects, the polymer is a branched
polymer.
[0097] In some aspects, the average number of alkylcarboxy
substitutions per silicone is between 1 and 15. In some aspects,
the average number of alkylcarboxy substitutions per silicone is
between 1 and 12. In some aspects, the average number of
alkylcarboxy substitutions per silicone is 1, 2, 3, 4, 5, 6, 7, 8,
9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25,
26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42,
43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59,
or 60.
[0098] In some aspects, the average number of crosslinks between
linear or branched silicones is between 1 and 15. In some aspects,
the average number of crosslinks between linear or branched
silicones is between 1 and 12. In some aspects, the average number
of crosslinks between linear or branched silicones is 1, 2, 3, 4,
5, 6, 7, 8, 9, 10, 11, or 12.
[0099] In some aspects, the polymer is prepared by a method
comprising reacting:
[0100] (a) a Si--H functional compound of formula (I):
M.sup.H.sub.aM.sub.bD.sup.H.sub.cD.sub.dT.sup.H.sub.eT.sub.fQ.sub.g
(I)
[0101] wherein: [0102] M.sup.H=R.sup.1R.sup.2HSiO.sub.1/2; [0103]
M=R.sup.3R.sup.4R.sup.5SiO.sub.1/2; [0104]
D.sup.H=R.sup.6HSiO.sub.2/2; [0105] D=R.sup.7R.sup.8SiO.sub.2/2;
[0106] T.sup.H=HSiO.sub.3/2; [0107] T=R.sup.9SiO.sub.3/2; and
[0108] Q=SiO.sub.4/2;
[0109] wherein [0110] R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5,
R.sup.6, R.sup.7, R.sup.8, and R.sup.9 are independently an
aliphatic, aromatic, or fluoro monovalent hydrocarbon having from 1
to 60 carbon atoms; and [0111] a, b, c, d, e, f, and g are
independently zero or a positive integer, such that
2.ltoreq.a+b+c+d+e+f+g.ltoreq.6000 and when a'+c'+e'=2,
a+c+e>2;
[0112] (b) a carboxy functional olefin of formula (II):
##STR00005##
[0113] wherein [0114] R' is hydrogen, --Si(R.sup.a).sub.3 wherein
R.sup.a is an aliphatic monovalent hydrocarbon, or an aliphatic,
aromatic or fluoro monovalent hydrocarbon; [0115] n is
0.ltoreq.n.ltoreq.30; and
[0116] (c) a silicone based alkenyl functional cross-linker of
formula (III) and/or a non-silicone based alkenyl functional
cross-linker of formula (IV):
M.sup.1.sub.a'M.sup.2.sub.b'D.sup.1.sub.c'D.sup.2.sub.d'T.sup.1.sub.e'T.-
sup.2.sub.f'Q.sub.g' (III),
##STR00006##
[0117] wherein: [0118] M.sup.1=R.sup.10R.sup.11R.sup.12SiO.sub.1/2;
[0119] M.sup.2=R.sup.13R.sup.14R.sup.15SiO.sub.1/2; [0120]
D.sup.1=R.sup.16R.sup.17SiO.sub.2/2; [0121]
D.sup.2=R.sup.18R.sup.19SiO.sub.2/2; [0122]
T.sup.1=R.sup.20SiO.sub.3/2; [0123] T.sup.2=R.sup.21SiO.sub.3/2;
and [0124] Q=SiO.sub.4/2;
[0125] wherein [0126] R.sup.11, R.sup.12, R.sup.13, R.sup.14,
R.sup.15, R.sup.17, R.sup.18, R.sup.19, and R.sup.21, are
independently an aliphatic, aromatic, or fluoro monovalent
hydrocarbon having from 1 to 60 carbon atoms; [0127] R.sup.10,
R.sub.16 ,and R.sup.20 are each a monovalent radical containing at
least one terminal olefin bond; a', b', c', d', e', f', and g' are
independently zero or a positive integer, such that
2.ltoreq.a'+b'+c'+d'+e'+f'+g'.ltoreq.6000 and when a+c+e=2,
a'+c'+e'>2; and [0128] Z is an aliphatic hydrocarbon with 1 to
60 carbon atoms.
[0129] The polymer can be prepared by mixing the components in any
order. Additionally, each component can be added simultaneously or
sequentially, or as batch or semi-batch preparations.
[0130] The reaction between the Si--H functional compound of
formula (I), carboxy functional olefin of formula (II), and
silicone based alkenyl functional cross-linker of formula (III)
and/or non-silicone based alkenyl functional cross-linker of
formula (IV) occurs in the presence of a suitable solvent. The
suitable solvent can be a low viscosity silicone fluid or a
volatile silicone fluid. Examples of suitable solvents include, but
are not limited to isodecane, isohexadecane, squalane,
hemisqualane, hydrogenated polyisobutene, jojoba,
cylcopentasiloxane, dimethicone, bis-phenylpropyl dimethicone,
octyldodecyl neopentanoate, oleyl oleate, oleyl alcohol,
isomyristyl alcohol, or combinations thereof.
[0131] In some aspects, the reaction between the Si--H compound of
formula (I), the carboxy functional olefin of formula (II) and the
alkenyl functional cross-linker of formula (III) and/or (IV) occurs
in the presence of at least one precious metal catalyst selected
from the group consisting of a rhodium, ruthenium, palladium,
osmium, iridium, iron, and platinum catalyst. In some aspects, at
least one of the platinum catalysts is selected from the group
consisting of (PtCl.sub.2Olefin), H(PtCl.sub.3Olefin), platinic
chloride, chloroplatinic acid, bis(acetylacetonato)platinum,
(.eta.15-Cyclopentadienyl)trialkylplatinum,
1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene-1,3-divinyl-1,1,3,3-tetr-
amethyldisiloxaneplatinum(0),
1,3-bis(cyclohexyl)imidazole-2-ylidene-1,3-divinyl
-1,1,3,3-tetramethyldisiloxaneplatinum(0), Pt.sub.2(dba).sub.3,
Pt.sub.2(dvs).sub.3, Pt(OAc).sub.2, Pt(acac).sub.2,
Na.sub.2PtCl.sub.6, K.sub.2PtCl.sub.6, platinum carbonate, platinum
nitrate, 1,5-cyclooctadienedimethylplatinum(II), platinum
perchlorate, amine complexes of the platinum ammonium
hexachloropalladate(IV), a cyclopropane complex of platinum
chloride, and a complex formed from chloroplatinic acid.
[0132] In some aspects, the platinum containing material can be a
complex formed from chloroplatinic acid with up to 2 moles per gram
of platinum of a member selected from the class consisting of
alcohols, ethers, aldehydes and mixtures of the above as described
in U.S. Pat. No. 3,220,972 hereby incorporated by reference. The
catalysts most specifically used herein are described in U.S. Pat.
Nos. 3,715,334; 3,775,452; and 3,814,730 to Karstedt. Additional
background concerning the art may be found at J. L. Spier,
"Homogeneous Catalysis of Hydrosilation by Transition Metals, in
Advances in Organometallic Chemistry, volume 17, pages 407 through
447, F. G. A. Stone and R. West editors, published by the Academic
Press (New York, 1979). In some aspects, the platinum catalyst is a
soluble complex form.
[0133] The amount of precious metal catalyst utilized in the
reaction can range from between about 0.1 and about 10,000 ppm. In
some aspects, the amount of precious metal catalyst can range from
between about 1 and about 1,000 ppm. In some aspects, the amount of
precious metal catalyst can range from between about 1 and 500 ppm.
In some aspects, the amount of precious metal catalyst can range
from between about 1 and 250 ppm. In some aspects, the amount of
precious metal catalyst can range from between about 1 and 100
ppm.
[0134] In some aspects, one or more of R.sup.1, R.sup.2, R.sup.3,
R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, and R.sup.9 is an
aliphatic, aromatic, or fluoro monovalent hydrocarbon. In some
aspects, one or more of R.sup.1, R.sup.2, R.sup.3, R.sup.4,
R.sup.5, R.sup.6, R.sup.7, R.sup.8, and R.sup.9 is a
C.sub.1-C.sub.30 monovalent hydrocarbon. In some aspects, one or
more of R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6,
R.sup.7, R.sup.8, and R.sup.9 is a C.sub.1-C.sub.18 monovalent
hydrocarbon. In some aspects, one or more of R.sup.1, R.sup.2,
R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, and R.sup.9
is a C.sub.1-C.sub.12 or C.sub.1-C.sub.6 monovalent hydrocarbon.
Examples of monovalent hydrocarbons for R.sup.1, R.sup.2, R.sup.3,
R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, and R.sup.9 isopropyl,
n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neo-pentyl,
tert-pentyl, hexyl (e.g., n-hexyl), heptyl (e.g., n-heptyl), octyl
(e.g., n-octyl, isocytyl), 2,2,4-trimethylpentyl, nonyl (n-decyl),
decyl, cycloalkyl (e.g., cyclopentyl, cyclohexyl, cycloheptyl, and
methylcyclohexyl), phenyl, naphthyl, o-tolyl, m-tolyl, p-tolyl,
xylyl, ethylphenyl, benzyl, any of which can be optionally
substituted by one or more fluoro atoms.
[0135] In some aspects, a, b, c, d, e, f, and g are
2.ltoreq.a+b+c+d+e+f+g.ltoreq.4000. In some aspects, a, b, c, d, e,
f, and g are 2.ltoreq.a+b+c+d+e+f+g.ltoreq.2000. In some aspects,
a, b, c, d, e, f, and g are 2.ltoreq.a+b+c+d+e+f+g.ltoreq.1000. In
some aspects, a, b, c, d, e, f, and g are
2.ltoreq.a+b+c+d+e+f+g.ltoreq.1500. In some aspects, a, b, c, d, e,
f, and g are 2.ltoreq.a+b+c+d+e+f+g.ltoreq.250. In some aspects, a,
c, and e are 2.ltoreq.a+c+e.ltoreq.120. In some aspects, a, c, and
e are 2.ltoreq.a+c+e.ltoreq.100.
[0136] In some aspects, R' is R.sup.1 or a combination of R.sup.1
and --Si(R.sup.a).sub.3 wherein R.sup.a is an aliphatic monovalent
hydrocarbon. In some aspects, R.sup.a is a C.sub.1-C.sub.12 group.
In some aspects, R.sup.a is a C.sub.1-C.sub.8 group. In some
aspects, R.sup.a is selected from the group consisting of methyl,
ethyl, propyl (n-propyl or isopropyl), butyl (e.g. n-butyl,
tert-butyl), pentyl (e.g., n-pentyl, isopentyl), hexyl (e.g.,
n-hexyl), and heptyl (e.g., n-heptyl). In some aspects, R.sup.a is
methyl. In some aspects, R' is ethyl. In some aspects, R' is
heptyl. In some aspects, R' is hydrogen.
[0137] In some aspects, R.sup.11, R.sup.12, R.sup.13, R.sup.14,
R.sup.15, R.sup.17, R.sup.18, R.sup.19, and R.sup.21, are
independently an aliphatic, aromatic, or fluoro monovalent
hydrocarbon having from 1 to 60 carbon atoms. In some aspects, one
or more of R.sup.11, R.sup.12, R.sup.13, R.sup.14, R.sup.15,
R.sup.17, R.sup.18, R.sup.19, and R.sup.21 is a C.sub.1-C.sub.30
monovalent hydrocarbon. In some aspects, one or more of R.sup.11,
R.sup.12, R.sup.13, R.sup.14, R.sup.15, R.sup.17, R.sup.18,
R.sup.19, and R.sup.21 is a C.sub.1-C.sub.18 monovalent
hydrocarbon.
[0138] In some aspects, one or more of R.sup.11, R.sup.12,
R.sup.13, R.sup.14, R.sup.15, R.sup.17, R.sup.18, R.sup.19, and
R.sup.21 an aliphatic monovalent hydrocarbon. In some aspects, one
or more of R.sup.11, R.sup.12, R.sup.13, R.sup.14, R.sup.15,
R.sup.17, R.sup.18, R.sup.19, and R.sup.21 is selected from the
group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl,
isobutyl, tert-butyl, n-pentyl, isopentyl, neo-pentyl, tert-pentyl,
hexyl, heptyl, octyl, nonyl, decyl, and cycloalkyl. In some
aspects, one or more of R.sup.11, R.sup.12, R.sup.13, R.sup.14,
R.sup.15, R.sup.17, R.sup.18, R.sup.19, and R.sup.21 is selected
from the group consisting of n-hexyl, n-heptyl, n-octyl, isooctyl,
2,2,4-trimethylpentyl, n-nonyl, n-decyl, cyclopentyl, cyclohexyl,
cycloheptyl, and methylcyclohexyl.
[0139] In some aspects, one or more of R.sup.11, R.sup.12,
R.sup.13, R.sup.14, R.sup.15, R.sup.17, R.sup.18, R.sup.19, and
R.sup.21 is an aromatic monovalent hydrocarbon. In some aspects,
one or more of R.sup.11, R.sup.12, R.sup.13, R.sup.14, R.sup.15,
R.sup.17, R.sup.18, R.sup.19, and R.sup.21 is selected from the
group consisting of phenyl, naphthyl, o-tolyl, m-tolyl, p-tolyl,
xylyl, ethylphenyl, and benzyl.
[0140] In some aspects, one or more of R.sup.11, R.sup.12,
R.sup.13, R.sup.14, R.sup.15, R.sup.17, R.sup.18, R.sup.19, and
R.sup.21 is a fluoro monovalent hydrocarbon.
[0141] In some aspects, a', b', c', d', e', f', and g' are
2.ltoreq.a'+b'+c'+d'+e'+f'+g'.ltoreq.4000. In some aspects, a', b',
c', d', e', f', and g' are
2.ltoreq.a'+b'+c'+d'+e'+f'+g'.ltoreq.3000. In some aspects, a', b',
c', d', e', f', and g' are
2.ltoreq.a'+b'+c'+d'+e'+f'+g'.ltoreq.2000. In some aspects, a', b',
c', d', e', f', and g' are
2.ltoreq.a'+b'+c'+d'+e'+f'+g'.ltoreq.1000. In some aspects, a', b',
c', d', e', f, and g' are 2.ltoreq.a'+b'+c'+d'+e'+f'+g'.ltoreq.500.
In some aspects, a', c', and e' are 2.ltoreq.a'+c'+e'.ltoreq.120.
In some aspects, a', c', and e' are 2.ltoreq.a'+c'+e'.ltoreq.100.
In some aspects, a'=2, d'=75-600, and b'=c'=e'=f'=g'=0.
[0142] In some aspects, Z is --(CHR.sup.22).sub.m-- or
--(CH.sub.2CHR.sup.23O).sub.k--, and m and k are positive integers,
such that 1.ltoreq.m.ltoreq.60 and 1.ltoreq.k.ltoreq.500, and
R.sup.22 and R.sup.23 are independently hydrogen or monovalent
hydrocarbon having from 1 to 60 carbon atoms. In some aspects, Z is
--(CHR.sup.22).sub.m--, m is 1-30, and R.sup.22 is from 1 to 30
carbon atoms. In some aspects, Z is --(CHR.sup.22).sub.m--, m is
1-18, and R.sup.16 is from 1 to 20 carbon atoms. In some aspects, Z
is --(CH.sub.2CHR.sup.23O).sub.k--, k is 1-250, and R.sup.23 is
from 1 to 30 carbon atoms. In some aspects, Z is
--(CH.sub.2CHR.sup.23O).sub.k--, k is 1-100, and R.sup.23 is from 1
to 20 carbon atoms.
[0143] In some aspects, the polymer is in a pure carboxy alkyl
ester form. In some aspects, the polymer is in combination of a
carboxy alkyl ester and salt (or acid) form. In some aspects, a
cation of the salt form is independently selected from alkali
metals, alkaline earth metals, transition metals, rare earth
metals, metals, metal complexes, quaternary ammonium and
phosphonium groups, organic cations, alkyl cations, cationic
hydrocarbons, cationic polymers, or zwitterions.
[0144] The disclosure also relates to a product prepared by any of
the methods described herein.
Personal Care Compositions
[0145] The disclosure additionally relates to personal care
compositions comprising (a) a composition or product described
herein; and (b) one or more personal care components. In one
aspect, the personal care composition comprises a solvent.
[0146] In one aspect herein, the silicone compositions described
herein are self-emulsifying. In another aspect, the personal care
composition may be further processed under low to high shear to
adjust the viscosity and sensory feel of the composition. This can
be achieved, for example, by subjecting the composition to a
moderate to high shearing force. High shear may be applied using,
for example, a Sonolator apparatus, a Gaulin Homogenizer or a Micro
Fluidizer apparatus. One or more carrier solvent may be added to
the silicone composition prior to the shearing.
[0147] In one aspect, the personal care composition is a solid,
typically having a creamy consistency, wherein the silicone polymer
acts as a means for gelling the fluid to reversibly impart
characteristics of a solid to the fluid. At rest, the personal care
composition exhibits the properties of a solid gel material. The
personal care composition can exhibit high stability and resistance
to syneresis so that the personal care composition exhibits little
or no tendency for fluid to flow from the personal care
composition. The high stability and syneresis resistance persists
with prolonged aging of the personal care compositions.
[0148] However, the solvent included in the personal care
composition can be released from the polymers described herein by
subjecting the personal care composition to a shearing force, such
as, for example, by rubbing the composition between one's fingers,
to provide improved sensory feel characteristic of the fluid
component of the silicone material. Water (or a water equivalent
such as a non-aqueous hydroxylic solvent), siloxane, hydrocarbon,
linear or cyclic, or lipophilic fluid (oil swelling agent, oil
swellable) can be used as the solvent which may function as a
swelling agent. Lipophilic fluids suitable for use as the solvent
component of the personal care composition are those described
herein. In one aspect, the solvent component of the personal care
composition exhibits a viscosity of below 1,000 cSt. In one aspect,
the solvent component of the personal care composition exhibits a
viscosity below 500 cSt. In one aspect, the solvent component of
the personal care composition exhibits a viscosity of below 250
cSt. In one aspect, the solvent component of the personal care
composition exhibits a viscosity of below 100 cSt, at 25.degree.
C.
[0149] In one aspect, the polymers described herein are soluble in
various fluid components, and are capable of thickening the
solvent. The amount of crosslinking present in the polymers
described herein may be characterized with respect to the degree of
thickening exhibited by the polymer in the solvent.
[0150] In another aspect, the cross linked structure of the
polymers described herein is effective to allow the polymer to be
swollen by a low molecular weight fluid, such as a silicone fluid,
hydrophobic oil, or silicone and hydrocarbon fluid, such as, for
example, decamethylcyclopentasiloxane, from its original volume to
a swollen volume.
[0151] The polymers described herein can be utilized as prepared or
as the hydrophobic component in a personal care composition that is
an emulsion. Emulsions comprise at least two immiscible phases. One
immiscible phase is continuous and the other is discontinuous. In
one aspect, the non-miscible phase (immiscible phase) is aqueous,
non-aqueous, or solid particulates.
[0152] Emulsions can be liquids with varying viscosities or solids.
The particle size of the emulsions can make them microemulsions.
When sufficiently small, the microemulsions can be transparent. It
is also possible to prepare emulsions of emulsions which are
generally known as multiple emulsions.
[0153] Examples of suitable emulsions for personal care
compositions include: 1) aqueous emulsions where the discontinuous
phase comprises water and the continuous phase comprises a polymer
composition or product described herein; 2) aqueous emulsions where
the discontinuous phase comprises a polymer composition or product
described herein and the continuous phase comprises water; 3)
non-aqueous emulsions where the discontinuous phase comprises a
non-aqueous hydroxylic solvent and the continuous phase comprises a
polymer composition or product described herein; and 4) non-aqueous
emulsions where the continuous phase comprises a non-aqueous
hydroxylic organic solvent and the discontinuous phase comprises a
polymer composition or product described herein.
[0154] Examples of suitable non-aqueous hydroxylic organic solvents
in the emulsions containing a polymer composition or product
described herein include, but are not limited to, ethylene glycol,
ethanol, propyl alcohol, isopropyl alcohol, propylene glycol,
dipropylene glycol, tripropylene glycol, butylene glycol,
isobutylene glycol, methyl propane diol, glycerin, sorbitol,
polyethylene glycol, polypropylene glycol mono alkyl ethers,
polyoxyalkylene copolymers and mixtures thereof.
[0155] In one aspect, the polymers described herein are compatible
with a particulate additive. In one aspect, the particulate
additive is an inorganic particulate, polymeric latex, and/or a
pigment. In another aspect, the polymers are capable of suspending
these particles for a prolonged period in personal care
formulations.
[0156] Once the desired emulsion is prepared, the resulting
material is usually a high viscosity cream with good feel
characteristics and high absorbance of volatile solvents. The
emulsion can then be blended into personal care compositions for
hair care, skin care, and the like.
[0157] The personal care composition can be a personal care
application including deodorants, antiperspirants,
antiperspirant/deodorants, shaving products, skin lotions,
moisturizers, toners, bath products, cleansing products, hair care
products such as shampoos, conditioners, mousses, styling gels,
hair sprays, hair dyes, hair color products, hair bleaches, waving
products, hair straighteners, manicure products (e.g., nail polish,
nail polish remover, nail creams and lotions, cuticle softeners),
protective creams (e.g., sunscreen, insect repellent and anti-aging
products), color cosmetics (e.g., lipsticks, foundations, face
powders, eye liners, eye shadows, blushes, makeup, and mascaras).
The personal care application can also be a drug delivery system
for topical application of a medicinal composition that can be
applied to the skin.
[0158] In one aspect, the personal care composition of the present
invention further comprises one or more personal care ingredients.
Suitable personal care ingredients include, for example,
emollients, moisturizers, humectants, pigments (e.g., pearlescent
pigments such as bismuth oxychloride and titanium dioxide coated
mica), colorants, fragrances, biocides, preservatives,
antioxidants, anti-fungal agents, antiperspirant agents,
exfoliants, hormones, enzymes, medicinal compounds, vitamins,
salts, electrolytes, alcohols, polyols, absorbing agents for
ultraviolet radiation, botanical extracts, surfactants, silicone
oils, organic oils, waxes, film formers, thickening agents (e.g.,
fumed silica or hydrated silica), particulate fillers (e.g., talc,
kaolin, starch, modified starch, mica, nylon, clays, such as, for
example, bentonite and organo-modified clays).
[0159] In some aspects, the one or more personal care components
included in the personal care compositions are selected from the
group consisting of a humectant, emollient, moisturizer, pigment,
colorant, fragrance, biocide, preservative, antioxidant,
anti-fungal agent, antiperspirant agent, exfoliant, hormone,
enzyme, medicinal compound, vitamin, salt, electrolyte, alcohol,
polyol, absorbing agent for ultraviolet radiation, botanical
extract, surfactant, silicone oil, organic oil, wax, film former,
and thickening agent. In some aspects, the one or more emollients
is selected from the group consisting of triglyceride esters, wax
esters, alkyl or alkenyl ester of fatty acids, polyhydric alcohol
esters, and mixtures thereof. In some aspects, the one or more
personal care components is a silicone oil, an organic oil, or
mixtures thereof.
[0160] In one aspect, the personal care composition is an
antiperspirant composition that comprises a polymer composition or
product described herein and one or more active antiperspirant
agents. Suitable antiperspirant agents include, but are not limited
to, the Category I active antiperspirant ingredients listed in the
U.S. Food and Drug Administration's Oct. 10, 1993 Monograph on
antiperspirant drug products for over-the-counter human use
including aluminum halides, aluminum hydroxyhalides, for example,
aluminum chlorohydrate, and complexes or mixtures thereof with
zirconyl oxyhalides and zirconyl hydroxyhalides, (e.g.,
aluminum-zirconium chlorohydrate, and aluminum zirconium glycine
complexes, such as aluminum zirconium tetrachlorohydrex gly).
[0161] In another aspect, the personal care composition is a skin
care composition comprising a polymer composition or product
described herein, and a vehicle, such as a silicone oil or an
organic oil. The skin care composition can also include emollients,
such as triglyceride esters, wax esters, alkyl or alkenyl esters of
fatty acids or polyhydric alcohol esters, pigments, vitamins (e.g.,
Vitamin A, Vitamin C and Vitamin E), sunscreen or sunblock
compounds (e.g., titanium dioxide, zinc oxide, oxybenzone,
octylmethoxy cinnamate, butylmethoxy dibenzoylm ethane,
p-aminobenzoic acid and octyl dimethyl-p-aminobenzoic acid).
[0162] In yet another aspect, the personal care composition is a
color cosmetic composition such as a lipstick, a makeup or mascara.
The color cosmetic composition comprises a polymer composition or
product described herein and a coloring agent (e.g., pigment,
water-soluble dye, or liposoluble dye).
[0163] In still yet another aspect, the personal care composition
comprises a polymer composition or product described herein and
fragrant materials. The fragrant materials can be fragrant
compounds, encapsulated fragrant compounds or fragrance releasing
compounds that either the neat compounds or are encapsulated.
EXAMPLES
[0164] The following synthetic examples (1-22), and formulation
examples (F1-F10) and Tables 3-12 are part of the invention, and
they are illustrative, but not limiting, of the methods of the
present invention. Other suitable modifications and adaptations of
the variety of conditions and parameters normally encountered in
the field, and which are obvious to those skilled in the art, are
within the spirit and scope of the invention.
Synthetic Example 1
[0165] A poly(dimethylhydrosiloxy)silicate (8.86 g, 79.74 mmol),
silyl undecylenic acid ester (11.97 g, 46.4 mmol), ethyl
10-undecylenate (10.15 g, 47.8 mmol), a vinyl terminal
polydimethylsiloxane (45.85 g, 7.97 mmol), hemisqualane (119.79 g)
and platinum(0) -1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex
(0.002 g Pt) were added into a reactor. The reactor was closed and
the air inside was replaced by flashing with nitrogen. Then the
mixture was stirred at room temperature for an hour and at
85.degree. C. for 3 hours when the entire reaction mixture was
transformed into a viscous gel, and then deionized water (2.3 g)
was added, and continued to stir at 85.degree. C. for an hour to
free up the silyl protected carboxylic acid. Then the reaction
mixture was vacuum stripped at 85.degree. C. and 150 mmHg for 30
minutes when the product was obtained as a viscous gel.
Synthetic Example 2
[0166] A poly(dimethylhydrosiloxy)silicate (8.86 g, 79.74 mmol),
silyl undecylenic acid ester (5.25 g, 46.4 mmol), ethyl
10-undecylenate (16.0 g, 75.36 mmol), a vinyl terminal
polydimethylsiloxane (45.85 g, 7.97 mmol), hemisqualane (113.94 g)
and platinum(0) -1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex
(0.002 g Pt) were added into a reactor. The reactor was closed and
the air inside was replaced by flashing with nitrogen. Then the
mixture was stirred at room temperature for an hour and at
85.degree. C. for 3 hours when the entire reaction mixture was
transformed into a viscous gel, and then deionized water (1.5 g)
was added, and continued to stir at 85.degree. C. for an hour to
free up the silyl protected carboxylic acid. Then the reaction
mixture was vacuum stripped at 85.degree. C. and 150 mmHg for 30
minutes when the product was obtained as a viscous gel.
Synthetic Example 3
[0167] A poly(dimethylhydrosiloxy)silicate (8.86 g, 79.74 mmol),
silyl undecylenic acid ester (8.2 g, 31.8 mmol), ethyl
10-undecylenate (13.5 g, 63.5 mmol), a vinyl terminal
polydimethylsiloxane (45.85 g, 7.97 mmol), hemisqualane (114.6 g)
and platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex
(0.002 g Pt) were added into a reactor. The reactor was closed and
the air inside was replaced by flashing with nitrogen. Then the
mixture was stirred at room temperature for an hour and at
85.degree. C. for 3 hours when the entire reaction mixture was
transformed into a viscous gel, and then deionized water (2.0 g)
was added, and continued to stir at 85.degree. C. for an hour to
free up the silyl protected carboxylic acid. Then the reaction
mixture was vacuum stripped at 85.degree. C. and 150 mmHg for 30
minutes when the product was obtained as a viscous gel.
Synthetic Example 4
[0168] A poly(dimethylhydrosiloxy)silicate (8.86 g, 79.74 mmol),
silyl undecylenic acid ester (11.0 g, 42.68 mmol), ethyl
10-undecylenate (13.5 g, 63.5 mmol), a vinyl terminal
polydimethylsiloxane (45.85 g, 7.97 mmol), hemisqualane (118.8 g)
and platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex
(0.002 g Pt) were added into a reactor. The reactor was closed and
the air inside was replaced by flashing with nitrogen. Then the
mixture was stirred at room temperature for an hour and at
85.degree. C. for 3 hours when the entire reaction mixture was
transformed into a viscous gel, and then deionized water (2.3 g)
was added, and continued to stir at 85.degree. C. for an hour to
free up the silyl protected carboxylic acid. Then the reaction
mixture was vacuum stripped at 85.degree. C. and 150 mmHg for 30
minutes when the product was obtained as a viscous gel.
Synthetic Example 5
[0169] A poly(dimethylhydrosiloxy)silicate (8.86 g, 79.74 mmol),
silyl undecylenic acid ester (5.18 g, 19.98 mmol), ethyl
10-undecylenate (13.5 g, 63.5 mmol), a vinyl terminal
polydimethylsiloxane (45.85 g, 7.97 mmol), hemisqualane (110.0 g)
and platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex
(0.002 g Pt) were added into a reactor. The reactor was closed and
the air inside was replaced by flashing with nitrogen. Then the
mixture was stirred at room temperature for an hour and at
85.degree. C. for 3 hours when the entire reaction mixture was
transformed into a viscous gel, and then deionized water (1.2 g)
was added, and continued to stir at 85.degree. C. for an hour to
free up the silyl protected carboxylic acid. Then the reaction
mixture was vacuum stripped at 85.degree. C. and 150 mmHg for 30
minutes when the product was obtained as a viscous gel.
Synthetic Example 6
[0170] A poly(dimethylhydrosiloxy)silicate (8.86 g, 79.74 mmol),
silyl undecylenic acid ester (2.1 g, 8.1 mmol), ethyl
10-undecylenate (13.5 g, 63.5 mmol), a vinyl terminal
polydimethylsiloxane (45.85 g, 7.97 mmol), hemisqualane (105.46 g)
and platinum(0) -1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex
(0.002 g Pt) were added into a reactor. The reactor was closed and
the air inside was replaced by flashing with nitrogen. Then the
mixture was stirred at room temperature for an hour and at
85.degree. C. for 3 hours when the entire reaction mixture was
transformed into a viscous gel, and then deionized water (0.5 g)
was added, and continued to stir at 85.degree. C. for an hour to
free up the silyl protected carboxylic acid. Then the reaction
mixture was vacuum stripped at 85.degree. C. and 150 mmHg for 30
minutes when the product was obtained as a viscous gel.
Synthetic Example 7
[0171] A poly(dimethylhydrosiloxy)silicate (8.86 g, 79.74 mmol),
silyl undecylenic acid ester (5.15 g, 19.98 mmol), heptyl
10-undecylenate (17.6 g, 62.3 mmol), a vinyl terminal
polydimethylsiloxane (45.85 g, 7.97 mmol), hemisqualane (116.19 g)
and platinum(0) -1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex
(0.002 g Pt) were added into a reactor. The reactor was closed and
the air inside was replaced by flashing with nitrogen. Then the
mixture was stirred at room temperature for an hour and at
85.degree. C. for 3 hours when the entire reaction mixture was
transformed into a viscous gel, and then deionized water (1.2 g)
was added, and continued to stir at 85.degree. C. for an hour to
free up the silyl protected carboxylic acid. Then the reaction
mixture was vacuum stripped at 85.degree. C. and 150 mmHg for 30
minutes when the product was obtained as a viscous gel.
Synthetic Example 8
[0172] A poly(dimethylhydrosiloxy)silicate (8.86 g, 79.74 mmol),
silyl undecylenic acid ester (5.15 g, 19.98 mmol), heptyl
10-undecylenate (20.0 g, 70.8 mmol), a vinyl terminal
polydimethylsiloxane (45.85 g, 7.97 mmol), hemisqualane (119.79 g)
and platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex
(0.002 g Pt) were added into a reactor. The reactor was closed and
the air inside was replaced by flashing with nitrogen. Then the
mixture was stirred at room temperature for an hour and at
85.degree. C. for 3 hours when the entire reaction mixture was
transformed into a viscous gel, and then deionized water (1.2 g)
was added, and continued to stir at 85.degree. C. for an hour to
free up the silyl protected carboxylic acid. Then the reaction
mixture was vacuum stripped at 85.degree. C. and 150 mmHg for 30
minutes when the product was obtained as a viscous gel.
Synthetic Example 9
[0173] A poly(dimethylhydrosiloxy)silicate (8.86 g, 79.74 mmol),
silyl undecylenic acid ester (10.0 g, 38.8 mmol), heptyl
10-undecylenate (14.5 g, 51.3 mmol), a vinyl terminal
polydimethylsiloxane (45.85 g, 7.97 mmol), hemisqualane (118.8 g)
and platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex
(0.002 g Pt) were added into a reactor. The reactor was closed and
the air inside was replaced by flashing with nitrogen. Then the
mixture was stirred at room temperature for an hour and at
85.degree. C. for 3 hours when the entire reaction mixture was
transformed into a viscous gel, and then deionized water (1.4 g)
was added, and continued to stir at 85.degree. C. for an hour to
free up the silyl protected carboxylic acid. Then the reaction
mixture was vacuum stripped at 85.degree. C. and 150 mmHg for 30
minutes when the product was obtained as a viscous gel.
Synthetic Example 10
[0174] A poly(dimethylhydrosiloxy)silicate (8.86 g, 79.74 mmol),
silyl undecylenic acid ester (10.0 g, 38.8 mmol), heptyl
10-undecylenate (18.5 g, 65.49 mmol), a vinyl terminal
polydimethylsiloxane (45.85 g, 7.97 mmol), hemisqualane (124.8 g)
and platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex
(0.002 g Pt) were added into a reactor. The reactor was closed and
the air inside was replaced by flashing with nitrogen. Then the
mixture was stirred at room temperature for an hour and at
85.degree. C. for 3 hours when the entire reaction mixture was
transformed into a viscous gel, and then deionized water (1.4 g)
was added, and continued to stir at 85.degree. C. for an hour to
free up the silyl protected carboxylic acid. Then the reaction
mixture was vacuum stripped at 85.degree. C. and 150 mmHg for 30
minutes when the product was obtained as a viscous gel.
Synthetic Example 11
[0175] A poly(dimethylhydrosiloxy)silicate (8.86 g, 79.74 mmol),
silyl undecylenic acid ester (7.5 g, 29.1 mmol), heptyl
10-undecylenate (17.25 g, 61.09 mmol), a vinyl terminal
polydimethylsiloxane (45.85 g, 7.97 mmol), hemisqualane (119.19 g)
and platinum(0) -1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex
(0.002 g Pt) were added into a reactor. The reactor was closed and
the air inside was replaced by flashing with nitrogen. Then the
mixture was stirred at room temperature for an hour and at
85.degree. C. for 3 hours when the entire reaction mixture was
transformed into a viscous gel, and then deionized water (1.04 g)
was added, and continued to stir at 85.degree. C. for an hour to
free up the silyl protected carboxylic acid. Then the reaction
mixture was vacuum stripped at 85.degree. C. and 150 mmHg for 30
minutes when the product was obtained as a viscous gel.
Synthetic Example 12
[0176] A poly(dimethylhydrosiloxy)silicate (8.86 g, 79.74 mmol),
silyl undecylenic acid ester (10 g, 38.8 mmol), heptyl
10-undecylenate (16.0 g, 56.64 mmol), a vinyl terminal
polydimethylsiloxane (45.85 g, 7.97 mmol), hemisqualane (121.0 g)
and platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex
(0.002 g Pt) were added into a reactor. The reactor was closed and
the air inside was replaced by flashing with nitrogen. Then the
mixture was stirred at room temperature for an hour and at
85.degree. C. for 3 hours when the entire reaction mixture was
transformed into a viscous gel, and then deionized water (1.4 g)
was added, and continued to stir at 85.degree. C. for an hour to
free up the silyl protected carboxylic acid. Then the reaction
mixture was vacuum stripped at 85.degree. C. and 150 mmHg for 30
minutes when the product was obtained as a viscous oil.
Synthetic Example 13
[0177] A poly(dimethylhydrosiloxy)silicate (8.86 g, 79.74 mmol),
silyl undecylenic acid ester (10 g, 38.8 mmol), heptyl
10-undecylenate (14.0 g, 49.56 mmol), a vinyl terminal
polydimethylsiloxane (45.85 g, 7.97 mmol), hemisqualane (121.0 g)
and platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex
(0.002 g Pt) were added into a reactor. The reactor was closed and
the air inside was replaced by flashing with nitrogen. Then the
mixture was stirred at room temperature for an hour and at
85.degree. C. for 3 hours when the entire reaction mixture was
transformed into a viscous gel, and then deionized water (1.4 g)
was added, and continued to stir at 85.degree. C. for an hour to
free up the silyl protected carboxylic acid. Then the reaction
mixture was vacuum stripped at 85.degree. C. and 150 mmHg for 30
minutes when the product was obtained as a viscous gel.
Synthetic Example 14
[0178] A poly(dimethylhydrosiloxy)silicate (8.86 g, 79.74 mmol),
heptyl 10-undecylenate (25.0 g, 88.5 mmol), a vinyl terminal
polydimethylsiloxane (45.85 g, 7.97 mmol), hemisqualane (119.56 g)
and platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex
(0.002 g Pt) were added into a reactor. The reactor was closed and
the air inside was replaced by flashing with nitrogen. Then the
mixture was stirred at room temperature for an hour and 85.degree.
C. for 3 hours when the product was obtained as a viscous gel.
Synthetic Example 15
[0179] A poly(dimethylhydrosiloxy)silicate (8.86 g, 79.74 mmol),
silyl undecylenic acid ester (2.0 g, 7.76 mmol), heptyl
10-undecylenate (22.0 g, 77.88 mmol), a vinyl terminal
polydimethylsiloxane (45.85 g, 7.97 mmol), hemisqualane (118.06 g)
and platinum(0) -1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex
(0.002 g Pt) were added into a reactor. The reactor was closed and
the air inside was replaced by flashing with nitrogen. Then the
mixture was stirred at room temperature for an hour and at
85.degree. C. for 3 hours when the entire reaction mixture was
transformed into a viscous gel, and then deionized water (0.28 g)
was added, and continued to stir at 85.degree. C. for an hour to
free up the silyl protected carboxylic acid. Then the reaction
mixture was vacuum stripped at 85.degree. C. and 150 mmHg for 30
minutes when the product was obtained as a viscous gel.
Synthetic Example 16
[0180] A poly(dimethylhydrosiloxy)silicate (8.86 g, 79.74 mmol),
silyl undecylenic acid ester (7.0 g, 27.16 mmol), heptyl
10-undecylenate (18.0 g, 63.72 mmol), a vinyl terminal
polydimethylsiloxane (45.85 g, 7.97 mmol), hemisqualane (119.56 g)
and platinum(0) -1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex
(0.002 g Pt) were added into a reactor. The reactor was closed and
the air inside was replaced by flashing with nitrogen. Then the
mixture was stirred at room temperature for an hour and at
85.degree. C. for 3 hours when the entire reaction mixture was
transformed into a viscous gel, and then deionized water (1.0 g)
was added, and continued to stir at 85.degree. C. for an hour to
free up the silyl protected carboxylic acid. Then the reaction
mixture was vacuum stripped at 85.degree. C. and 150 mmHg for 30
minutes when the product was obtained as a viscous gel.
Synthetic Example 17
[0181] A polymethylhydrosiloxane (7.5 g, 125 mmol), silyl
undecylenic acid ester (5.0 g, 19.4 mmol), heptyl 10-undecylenate
(30.0 g, 106.2 mmol), a vinyl terminal polydimethylsiloxane (45.85
g, 7.97 mmol), hemisqualane (132.52 g) and platinum(0)
-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (0.002 g Pt)
were added into a reactor. The reactor was closed and the air
inside was replaced by flashing with nitrogen. Then the mixture was
stirred at room temperature for an hour and at 85.degree. C. for 3
hours when the entire reaction mixture was transformed into a
viscous gel, and then deionized water (0.7 g) was added, and
continued to stir at 85.degree. C. for an hour to free up the silyl
protected carboxylic acid. Then the reaction mixture was vacuum
stripped at 85.degree. C. and 150 mmHg for 30 minutes when the
product was obtained as soft gel powder. To this was added Element
14 PDMS 5 cst oil (1400.0 g) and mixed under high shear mixing
until a homogeneous gel was obtained.
Synthetic Example 18
[0182] A poly(dimethylhydrosiloxy)silicate (7.5 g, 67.5 mmol),
silyl undecylenic acid ester (7.18 g, 28.0 mmol), heptyl
10-undecylenate (20.0 g, 70.8 mmol), a vinyl terminal
polydimethylsiloxane (90.0 g, 3.96 mmol), hemisqualane (100 g) and
platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex
(0.005 g Pt) were added into a reactor. The reactor was closed and
the air inside was replaced by flashing with nitrogen. Then the
mixture was stirred at room temperature for an hour and at
85.degree. C. for 3 hours when the entire reaction mixture was
transformed into a viscous gel, and then deionized water (0.7 g)
was added, and continued to stir at 85.degree. C. for an hour to
free up the silyl protected carboxylic acid. Then the reaction
mixture was vacuum stripped at 85.degree. C. and 150 mmHg for 30
minutes when the product was obtained as a viscous gel.
Synthetic Example 19
[0183] A poly(dimethylhydrosiloxy)silicate (7.5 g, 67.5 mmol),
silyl undecylenic acid ester (4.0 g, 15.6 mmol), undecylenic acid
(2.3 g, 12.4 mmol), heptyl 10-undecylenate (20.0 g, 70.8 mmol), a
vinyl terminal polydimethylsiloxane (90.0 g, 3.96 mmol),
hemisqualane (100 g) and
platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex
(0.005 g Pt) were added into a reactor. The reactor was closed and
the air inside was replaced by flashing with nitrogen. Then the
mixture was stirred at room temperature for an hour and at
85.degree. C. for 3 hours when the entire reaction mixture was
transformed into a viscous gel, and then deionized water (0.7 g)
was added, and continued to stir at 85.degree. C. for an hour to
free up the silyl protected carboxylic acid. Then the reaction
mixture was vacuum stripped at 85.degree. C. and 150 mmHg for 30
minutes when the product was obtained as a viscous gel.
Synthetic Example 20
[0184] A polydimethylhydrosiloxane (3.75 g, 62.5 mmol), silyl
undecylenic acid ester (5.0 g, 19.45 mmol), heptyl 10-undecylenate
(25.0 g, 88.5 mmol), a vinyl terminal polydimethylsiloxane (57.5 g,
2.53 mmol), bis methallyl capped poly(ethylene glycol-co-propylene
glycol) containing 60% E0 and 40% PO (2.0 g, 1.32 mmol),
hemisqualane (150 g) and
platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex
(0.002 g Pt) were added into a reactor. The reactor was closed and
the air inside was replaced by flashing with nitrogen. Then the
mixture was stirred at room temperature for an hour and at
85.degree. C. for 3 hours when the entire reaction mixture was
transformed into a viscous gel, and then deionized water (0.7 g)
was added, and continued to stir at 85.degree. C. for an hour to
free up the silyl protected carboxylic acid. Then the reaction
mixture was vacuum stripped at 85.degree. C. and 150 mmHg for 30
minutes when the product was obtained as a viscous gel.
Synthetic Example 21
[0185] A poly(dimethylhydrosiloxy)silicate (7.5 g, 67.5 mmol),
silyl undecylenic acid ester (7.0 g, 27.2 mmol), hemisqualane (100
g) and platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane
complex (0.005 g Pt) were added into a reactor. The reactor was
closed and the air inside was replaced by flashing with nitrogen.
Then the mixture was stirred at room temperature for an hour and
added heptyl 10-undecylenate (20.0 g, 70.8 mmol), a vinyl terminal
polydimethylsiloxane (90.0 g, 3.96 mmol) and continued to mix under
shear at 85.degree. C. for 3 hours when the entire reaction mixture
was transformed into a viscous gel, and then deionized water (0.7
g) was added, and continued to stir at 85.degree. C. for an hour to
free up the silyl protected carboxylic acid. Then the reaction
mixture was vacuum stripped at 85.degree. C. and 150 mmHg for 30
minutes when the product was obtained as a viscous gel.
Synthetic Example 22
[0186] A poly(dimethylhydrosiloxy)silicate (7.5 g, 67.5 mmol),
silyl undecylenic acid ester (4.0 g, 15.6 mmol),
allyloxy(polyethyleneoxide) (6.82 g, 12.4 mmol), heptyl
10-undecylenate (20.0 g, 70.8 mmol), a vinyl terminal
polydimethylsiloxane (90.0 g, 3.96 mmol), hemisqualane (100 g) and
platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex
(0.005 g Pt) were added into a reactor. The reactor was closed and
the air inside was replaced by flashing with nitrogen. Then the
mixture was stirred at room temperature for an hour and at
85.degree. C. for 3 hours when the entire reaction mixture was
transformed into a viscous gel, and then deionized water (0.7 g)
was added, and continued to stir at 85.degree. C. for an hour to
free up the silyl protected carboxylic acid. Then the reaction
mixture was vacuum stripped at 85.degree. C. and 150 mmHg for 30
minutes when the product was obtained as a viscous gel.
Comparative Example 1
[0187] A commercially available traditional silicone gel containing
5 wt % active network were used as benchmark.
Comparative Example 2
[0188] Hemisqualane (94.38 g), a poly(dimethylhydrosiloxy)silicate
(8.86 g, 79.74 mmol) and silyl undecylenic acid ester (23.94 g,
95.5 mmol) were added into a reactor. To this mixture,
platinum(0)-1,3-divinyl-1,1,3,3 -tetram ethyl di siloxane complex
(0.002 g Pt) dissolved in hemisqualane (5 mL) was added. The
reactor was closed and the air inside was replaced by flashing with
nitrogen. The mixture was continued to slowly stir at room
temperature to facilitate the hydrosilylation of
poly(dimethylhydrosiloxy)silicate with the undecylenic acid ester.
Once the hydrosilylation with undecylenic acid ester was completed,
a vinyl terminal polydimethylsiloxane (45.85 g, 7.97 mmol)
dissolved in hemisqualane (23.60 g) and
platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex
(0.002 g Pt) were added. The reaction temperature was raised to
85.degree. C. and allowed to shear the mixture for additional 3
hours when the entire reaction mixture was transformed into a
viscous gel. To this was added deionized water (3.37 g) and
continued to stir at 85.degree. C. for an hour. Then the reaction
mixture was vacuum stripped at 85.degree. C. and 150 mmHg for 30
minutes when the product was obtained as a transparent gel.
Comparative Example 3
[0189] Hemisqualane (300.0 g), a polymethylhydrosiloxane copolymer
(24.0 g, 103.2 mmol) and silyl undecylenic acid ester (22.63 g,
88.25 mmol) were added into a reactor. To this mixture,
platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex
(0.005 g Pt) dissolved in hemisqualane (5 mL) was added. The
reactor was closed and the air inside was replaced by flashing with
nitrogen. The mixture was continued to slowly stir at room
temperature to facilitate the hydrosilylation of
poly(dimethylhydrosiloxy)silicate with the undecylenic acid ester.
Once the hydrosilylation with undecylenic acid ester was completed,
a vinyl terminal polydimethylsiloxane (206.0 g, 10.3 mmol) and
platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex
(0.005 g Pt) were added. The reaction temperature was raised to
85.degree. C. and allowed to shear the mixture for additional 3
hours when the entire reaction mixture was transformed into a
viscous gel. To this was added deionized water (6.37 g) and
continued to stir at 85.degree. C. for an hour. Then the reaction
mixture was vacuum stripped at 85.degree. C. and 150 mmHg for 30
minutes when the product was obtained as a viscous gel.
[0190] It is evident from the Tables 1 and 2, the cross-linked
silicone gel containing alkyl carboxylic esters has superior
compatibility and structuring properties with various natural and
synthetic oils compared to traditional and carboxylic acid
functional silicone gels. Therefore, these materials can help
broadening the applications scope of the silicone gel materials
across different products portfolio.
TABLE-US-00001 TABLE 1 Compatibility and structuring performance of
comparative materials Network COOH COOC.sub.nH.sub.2n+1 Content
content content Ingredients (%) (mmol/g) (mmol/g) CF1 CF2 CF3 CF4
CF5 CF6 CF7 CF8 CF9 CF10 CF11 CF12 Comparative 5 -- -- 1.0 1.0 1.0
1.0 Example 1 Comparative 40 0.477 -- 1.0 1.0 1.0 1.0 Example 2
Comparative 45 0.159 -- 1.0 1.0 1.0 1.0 Example 3 Element 14 -- --
-- 7.0 7.0 7.0 7.0 4.5 4.5 4.5 PDMS 5 Isononyl -- -- -- 9.0 9.0
Isononanoate Isopropyl -- -- -- 9.0 4.5 Myristate Caprylic/ -- --
-- 9.0 4.5 Capric Triglyceride Dibutyl -- -- -- 9.0 4.5 Adipate
Sunflower -- -- -- 2.0 Oil Jojoba Oil -- -- -- 2.0 Coconut Oil --
-- -- 2.0 Olive Oil -- -- -- 2.0 Total 10 10 10 10 10 10 10 10 10
10 10 10 Compatibility No No No No No No No No No No No No Oil No
No No No No No No No No No No No Structuring
TABLE-US-00002 TABLE 2 Compatibility and structuring performance of
comparative materials COOH COOC.sub.nH.sub.2n+1 Network content
content Ingredients Content (mmol/g) (mmol/g) F1 F2 F3 F4 F5 F6 F7
F8 F9 F10 F11 F12 Synthetic 40 0.099 0.353 1.0 1.0 Example 8
Synthetic 40 0.194 0.257 1.0 1.0 Example 9 Synthetic 40 -- 0.444
1.0 1.0 1.0 1.0 Example 14 Synthetic 40 0.039 0.395 1.0 1.0 Example
15 Synthetic 40 0.135 0.318 1.0 Example 16 Synthetic 5 0.022 0.120
1.0 Example 17 Element 14 -- -- -- 7.0 7.0 7.0 7.0 4.5 4.5 4.5 PDMS
5 Isononyl -- -- -- 9.0 9.0 Isononanoate Isopropyl -- -- -- 9.0 4.5
Myristate Caprylic/ -- -- -- 9.0 4.5 Capric Triglyceride Dibutyl --
-- -- 9.0 4.5 Adipate Sunflower -- -- -- 2.0 Oil Jojoba Oil -- --
-- 2.0 Coconut Oil -- -- -- 2.0 Olive Oil -- -- -- 2.0 Total 10 10
10 10 10 10 10 10 10 10 10 10 Compatibility Y Y Y Y Y Y Y Y Y Y Y Y
Oil Y Y Y Y Y Y Y Y Y Y Y Y Structuring
Formulation Example 1
Hair Protection Serum.
[0191] Procedure: [0192] All of the ingredients were added in a
beaker and mixed at room temperature until homogeneous.
TABLE-US-00003 [0192] TABLE 3 International Nomenclature of
Cosmetic Ingredients INGREDIENTS (INCI) Supplier % w/w SF 1202
Cyclopentasiloxane Momentive 66.55 Synthetic 7.50 Example 18
Isopropyl Croda 20.00 myristate SilSoft A + PEG-40/PPG-8 Momentve
Methylaminopropyl/ 0.50 Hydropropyl Dimethicone copolymer SilSoft
034 Caprylyl Methicone Momentive 5.00 20% Aqueous KOH 0.45 Total
100.00
Formulation Example 2
Repair Hair Oil.
[0193] Procedure: [0194] All of the ingredients were added in a
beaker and mixed at room temperature until homogeneous.
TABLE-US-00004 [0194] TABLE 4 INGREDIENTS INCI Supplier % w/w
Hemisqualane C13-15 Alkane Amyris Inc. 30.05 SF1202
Cyclopentasiloxane Momentive 50.00 SilSoft 034 Caprylyl Methicone
Momentive 10.00 Synthetic 7.50 Example 18 Almond Oil Prunus 1.00
amygdalus dulcis (almond) oil SilSoft CLX-E Dipropylene Momentive
1.00 Glycol (and) Polysilicone-29 20% Aqueous KOH 0.45 Total
100.00
Formulation Example 3
Nourishing Skin Essence.
[0195] Procedure: [0196] All of the ingredients were added in a
beaker and mixed at room temperature until homogeneous.
TABLE-US-00005 [0196] TABLE 5 INGREDIENTS INCI Supplier % w/w
Hemisqualane C13-15 Alkane Amyris Inc. 84.60 Synthetic 10.00
Example 18 Argan Oil Argania Spinosa 1.00 Kernel Oil Olive Oil Olea
Europaea 1.00 (olive) oil Jojoba Oil Simmondsia Chinensis 1.00
(Jojoba) Seed Oil Almond Oil Prunus amygdalus 1.00 dulcis (almond)
oil Vitamin E Acetate Tocopheryl Acetate 0.50 Fragrance 0.30 20%
Aqueous KOH 0.60 Total 100.00
Formulation Example 4
Honey Body Gel.
[0197] Procedure: [0198] All of the ingredients were added in a
beaker and mixed at room temperature until homogeneous.
TABLE-US-00006 [0198] TABLE 6 INGREDIENTS INCI Supplier % w/w
Hemisqualane C13-15 Alkane Amyris Inc. 56.40 Isododecane
Isododecane Sigma Aldrich 10.00 SilSoft One Momentive 20.00
Synthetic 10.00 Example 18 Argan Oil Argania Spinosa 1.00 Kernel
Oil Pigment (Mica (and) Titanium 0.70 Dioxide (and) Iron Oxides)
Tocopherol Acetate Tocopheryl Acetate 1.00 Fragrance 0.30 20%
Aqueous KOH 0.60 Total 100.00
Formulation Example 5
Shimmering Body Oil Gel.
[0199] Procedure: [0200] All of the ingredients were added in a
beaker and mixed at room temperature until homogeneous.
TABLE-US-00007 [0200] TABLE 7 INGREDIENTS INCI Supplier % w/w
Hemisqualane C13-15 Alkane Amyris Inc. 57.60 Almond Oil Prunus
amygdalus 5.00 dulcis (almond) oil Jojoba Oil Simmondsia Chinensis
5.00 (Jojoba) Seed Oil Synthetic 10.00 Example 18 Mineral Oil
Paraffinum Liquidum 20.00 Pigment Mica (and) Titanium 0.50 Dioxide
(and) Tin oxide Tocopherol Acetate Tocopheryl Acetate 1.00
Fragrance 0.30 20% Aqueous KOH 0.60 Total
Formulation Example 6
Baby Oil Gel.
[0201] Procedure: [0202] All of the ingredients were added in a
beaker and mixed at room temperature until homogeneous.
TABLE-US-00008 [0202] TABLE 8 INGREDIENTS INCI Supplier % w/w
Hemisqualane C13-15 Alkane Amyris Inc. 37.40 SF1202
Cyclopentasiloxane Momentive 20.00 Mineral Oil Paraffinum Liquidum
30.00 Synthetic 10.00 Example 18 Jojoba Oil Simmondsia Chinensis
1.00 (Jojoba) Seed Oil Shea Butter Butyrospermum 0.50 Parkii (Shea)
Butter Tocopherol Acetate Tocopherol Acetate 0.50 20% Aqueous KOH
0.60 Total 100.00
Formulation Example 7
Natural Massage Oil
[0203] Procedure: [0204] All of the ingredients were added in a
beaker and mixed at room temperature until homogeneous.
TABLE-US-00009 [0204] TABLE 9 INGREDIENTS INCI Supplier % w/w
Glycerine Glycerin Sigma Aldrich 18.90 Isononyl Isononyl 5.00
Isononanoate Isononanoate Hemisqualane C13-15 Alkane Amyris Inc.
35.00 Synthetic 10.00 Example 20 Sunflower Oil Helianthus Annuus
20.00 (Sunflower) Seed Oil Almond Oil Prunus amygdalus 5.00 dulcis
(almond) oil Jojoba Oil Simmondsia Chinensis 5.00 (Jojoba) Seed Oil
Tocopherol Acetate Tocopherol Acetate 0.50 20% Aqueous KOH 0.60
Total 100.00
Formulation Example 8
Anhydrous SPF 30 PA+++ Sunscreen Gel
[0205] Procedure: [0206] All of the ingredients were added in a
beaker and mixed at room temperature until homogeneous.
TABLE-US-00010 [0206] TABLE 10 INGREDIENTS INCI Supplier % w/w
SF1202 Cyclopentasiloxane Momentive 14.50 Isododecane Isododecane
Sigma 25.00 Aldrich Isononyl Isononanoate Isononyl Isononanoate
10.00 Isopropyl Myristate Isopropyl Myristate 5.00 Synthetic
Example 21 8.50 Octocrylene Octocrylene 10.00 Homosalate
3,3,5-Trimethylcyclohexyl 10.00 salicylate Ethylhexyl Salicylate
2-Ethylhexyl salicylate 5.00 Octyl- Octyl methoxycinnamate 7.50
methoxycinnamate Avobenzone Butyl Meth- 3.00 oxydibenzoylmethane
Tocopherol Acetate Tocopherol Acetate 0.50 Boron Nitride Boron
Nitride 1.00 20% Aqueous KOH 0.51 Total 100.00
Formulation Example 9
Natural Tinted Lip Balm.
[0207] Procedure: [0208] All of the ingredients were added in a
beaker and mixed at room temperature until homogeneous.
TABLE-US-00011 [0208] TABLE 11 INGREDIENTS INCI Supplier % w/w
Hemisqualane C13-15 Alkane Amyris Inc. 32.30 Isododecane
Isododecane 10.00 Castor Oil Ricinus communis 20.00 (Castor) Seed
Oil Synthetic 15.00 Example 18 Sunflower Oil Helianthus Annuus
20.00 (Sunflower) Seed Oil Tocopherol Acetate Tocopherol Acetate
0.50 Pigment Mica (and) Titanium 1.00 Dioxide (and) Tin oxide
Fragrance 0.30 20% Aqueous KOH 0.90 Total 100.00
Formulation Example 10
Anhydrous HD Foundation
[0209] Procedure: [0210] All of the ingredients were added in a
beaker and mixed at room temperature until homogeneous.
TABLE-US-00012 [0210] TABLE 12 INGREDIENTS INCI Supplier % w/w
Isododecane Isododecane Sigma-Aldrich 51.65 Synthetic 10.00 Example
21 Isononyl Isononyl 10.00 Isononanoate Isononanoate TiO.sub.2
Titanium dioxide 7.00 Red Iron Oxide Iron Oxide 0.50 Yellow Iron
Oxide Iron Oxide 0.80 Black Iron Oxide Iron Oxide 0.05 SS 4230
Cyclopentasiloxane (and) Momentive 3.00 Trimethylsiloxysilicate
Velvesil 125 Cyclopentasiloxane Momentive 15.00 (and) C30-45 Alkyl
Cetearyl Dimethicone Tospearl 3000 Polymethylsilsesquioxane
Momentive 2.00 20% Aqueous KOH 0.60 Total 100.00
* * * * *